Dual cured castable hybrid polyurethane/polyurea system for use in golf balls

ABSTRACT

Compositions for golf balls that include polyurethane and polyurea linkages and that are crosslinked in the soft segments of the polymer backbone. In particular, the compositions of the invention, which are based on a polyurethane and/or polyurea prepolymers, have improved crosslink density from the crosslinking between the soft, unsaturated segments of the polymer backbone. The curative blend includes at least one isocyanate-reactive component and a free radical initiator.

FIELD OF THE INVENTION

The present invention relates to compositions for golf balls thatinclude modified polyurethane and/or polyureas. In particular, thecompositions of the invention, which include a polymer backboneincluding urea linkages, urethane linkages, or a combination of bothtypes of linkages, are crosslinked both in the soft and hard segmentswith a curative including amino groups, hydroxy groups, or a combinationthereof, and a free radical initiator. The compositions of the inventionmay be used in any layer of a golf ball, e.g., an outer cover layer orinner cover layer, or may be used as a coating to be disposed over astructural outer layer of a golf ball.

BACKGROUND OF THE INVENTION

Golf ball manufacturers have been experimenting with various materialsand manufacturing methods for golf balls over the years in an attempt toimprove overall performance and durability and to further refine themanufacturing process.

For example, over the past years, golf ball manufacturers have beenusing ionomer resins for golf ball cover materials because of thedurability, rebound, and scuff resistance characteristics of thematerials. However, while ionomer resins are more durable than othertypes of golf ball layer materials, the same properties that result indurability also provide a hard “feel” and generally result in a lowerspin rate and, thus, lower control, due to the hardness of the material.

Alternatively, polyurethane compositions produce “soft” covers andtypically allow for greater control because of the increased spin.Because conventional polyurethane cover materials are typically formedof aromatic components, the ultraviolet degradation of the material,which leads to yellowing, led to the recent trend toward light stablecover materials, such as aliphatic polyurethane and polyurea materials.Whether aromatic or aliphatic in nature, however, the relative softnessof the polyurethane and polyurea materials introduces durability issues.

Further attempts to compensate for the “hard” feel of ionomer-coveredgolf balls and durability and adhesion issues with polyurethane-coveredand polyurea-covered golf balls have resulted in blends of hard ionomerresins, i.e., resins with hardness values of about 60 Shore D and above,with relatively softer polymeric materials. For example, blends of hardionomers with polyurethanes have been used to form intermediate layersand cover layers of golf balls. However, such blends generally haveprocessing difficulties associated with their use in the production ofgolf balls due to the incompatibility of the components. In addition,golf balls produced from these incompatible mixtures will have inferiorgolf ball properties such as poor durability, cut resistance, and thelike.

As such, a need exists in the golf ball art for materials that have theperformance benefits of polyurethane and polyurea, but higher hardnessand higher flexural modulus values, as well as improved hydrophobicity.In addition, golf balls having layers formed, at least in part, fromsuch compositions would be advantageous. The present invention addressessuch materials, methods of forming the materials, and portions of golfballs formed from these materials.

SUMMARY OF THE INVENTION

The present invention is directed to a golf ball including a core and acover, wherein the cover is formed from a composition including: aprepolymer including the reaction product of an isocyanate-containingcomponent and a first isocyanate-reactive component, wherein the firstisocyanate reactive component includes a conjugated diene hydrocarbonincluding at least two functional groups including amino groups, hydroxygroups, or a mixture thereof; and a curative blend including a secondisocyanate-reactive component and at least one free radical initiator,wherein the composition includes crosslinks between the hydrocarbons.The at least one free radical initiator may include peroxide.

In one embodiment, the isocyanate-containing component includes at leasttwo isocyanate groups. In another embodiment, the firstisocyanate-reactive component includes amine-terminated polybutadiene.For example, the amine-terminated polybutadiene may include primaryamino groups at the terminal ends of the polybutadiene.

In yet another embodiment, the first isocyanate-reactive componentincludes hydroxy-terminated polybutadiene. For example, thehydroxy-terminated polybutadiene may include primary hydroxy groups atthe terminal ends of the polybutadiene.

The present invention also relates to a golf ball including: a core; anda cover formed from a composition including: a prepolymer including: apolymer backbone including a conjugated diene; and a plurality ofterminal ends including isocyanate groups; a curative blend including anisocyanate-reactive component and a free radical initiator, wherein theisocyanate-reactive component is capable of reacting with the isocyanategroups and the free radical initiator is capable of crosslinking thepolymer backbone.

In one embodiment, the polymer backbone includes polybutadiene. Inanother embodiment, the free radical initiator includes peroxide. Instill another embodiment, the isocyanate-reactive component includes anamine-terminated component, a hydroxy-terminated component, or a mixturethereof. In this aspect of the invention, the prepolymer may includeurea linkages, urethane linkages, or a mixture thereof. In oneembodiment, the prepolymer consists essentially of urea linkages. In analternate embodiment, the prepolymer consists essentially of urethanelinkages. In yet another embodiment, the prepolymer includes both ureaand urethane linkages.

The present invention is directed to a golf ball including a core and acover, wherein the cover is formed from a composition including: aprepolymer including the reaction product of an isocyanate-containingcomponent and a first isocyanate-reactive component, wherein the firstisocyanate-reactive component includes a conjugated diene hydrocarbonincluding at least one functional amino group and at least onefunctional hydroxy group; and a curative blend including a secondisocyanate-reactive component and at least one free radical initiator,wherein the composition includes crosslinks between the hydrocarbons.The free radical initiator may include an organic peroxide.

In one embodiment, the isocyanate-containing component includes at leasttwo isocyanate groups. In another embodiment, the conjugated dienehydrocarbon includes polybutadiene. In yet another embodiment, thesecond isocyanate-reactive component includes an amine-terminatedcomponent, a hydroxy-terminated component, or a mixture thereof. Forexample, the second isocyanate-reactive component may include only aminogroups. Alternatively, the second isocyanate-reactive component mayinclude only hydroxy groups.

BRIEF DESCRIPTION OF THE DRAWINGS

Further features and advantages of the invention can be ascertained fromthe following detailed description that is provided in connection withthe drawing(s) described below:

FIG. 1 is a cross-sectional view of a two-piece golf hall, wherein thecover is formed from a composition of the invention;

FIG. 2 is a cross-sectional view of a multi-component golf ball, whereinat least one layer is formed from a composition of the invention;

FIG. 3 is a cross-sectional view of a multi-component golf ball having alarge core, wherein at least one layer is formed from a composition ofthe invention;

FIG. 4 is a cross-sectional view of a multi-component golf ballincluding a dual core and a dual cover, wherein at least one layer isformed from a composition of the invention;

FIG. 5 is a graphical illustration of the weight gain of golf balls ofthe invention over a four week period of submersion in water; and

FIG. 6 is a graphical illustration of loss of COR of golf bans of theinvention after a four week period of submersion in water.

DETAILED DESCRIPTION OF THE INVENTION

Because crosslinking in conventional castable reactive liquid materialsis limited to the hard segments, i.e., the isocyanate groups, theability to increase crosslinking density and, thus, hardness is limited.Thus, the present invention relates to compositions for use in golfballs that include polyurethane systems, polyurea systems, and mixturesthereof that are crosslinked both in the hard and soft segments of thepolymer. In particular, the compositions of the invention include thereaction product of an isocyanate-containing component and anisocyanate-reactive component that is subjected to a curing process thatinvolves a first curative that crosslinks the hard segments in thepolymer and a second curative that crosslinks the soft segments.

The compositions of the invention provide an alternative tothermoplastic materials, such as ionomers, that are typically used asouter covers on large core balls or inner covers on multilayer ballswith relatively soft covers. In fact, without being bound to anyparticular theory, golf balls that include the compositions of theinvention as cover layers or intermediate layers have improved moistureresistance and durability. In addition, the present invention exploresthe methods of making such compositions and the golf balls that areformed using the compositions in portions thereof.

The compositions of the invention can be used with a variety of golfball constructions. For example, the compositions of the invention maybe used as a cover layer in a two-piece ball with a large core, an outercover layer in a three-piece ball with a relatively thin inner coverlayer, an intermediate layer in a three-piece ball, or an inner coverlayer in a golf ball having dual cover layers. In addition, thecompositions of the invention may be used to form coatings for golfballs. The composition components, golf ball constructions, and layerand ball properties are discussed in greater detail below.

The Compositions of the Invention

The compositions of the invention include a prepolymer that is thereaction product of an isocyanate-containing component and anisocyanate-reactive component, which is crosslinked with a combinationof a curing agent and a free radical initiator. In particular, thereaction product of the isocyanate-containing component andisocyanate-reactive component produces a prepolymer includingpolyurethane linkages, polyurea linkages, or a combination thereof. Thecomponents of the composition are discussed below.

Prepolymer

The prepolymer used in the compositions of the invention may be based ona polyurethane, a polyurea, or a combination thereof. For example, theprepolymer may include urethane linkages, which is referred to herein asa polyurethane prepolymer, urea linkages, which is referred to herein asa polyurea prepolymer, or urethane and urea linkages, which is referredto herein as a hybrid prepolymer, each of which are discussed in moredetail below.

Polyurethane Prepolymer

When based on polyurethane, the prepolymer is a product formed by areaction between at least one isocyanate and at least onehydroxy-terminated component. The components of the polyurethaneprepolymer may be aromatic, aromatic-aliphatic, or aliphatic, whichprovide varying degrees of light stability. As used herein, aromaticaliphatic compounds should be understood as those containing an aromaticring, wherein the isocyanate group is not directly bonded to the ring.

Along a continuum, an aromatic composition is less light stable than anaromatic-aliphatic composition, which is less light stable than analiphatic composition. For example, an aliphatic composition madeaccording to the invention includes only saturated components, i.e.,components substantially free of unsaturated carbon-carbon bonds oraromatic groups, the use of which prevents yellowing over time. The term“saturated,” as used herein, refers to compositions having saturatedaliphatic and alicyclic polymer backbones, i.e., with no carbon-carbondouble bonds. It is important to note, however, that aromaticcompositions made according to the invention may include lightstabilizers to improve light stability. Thus, light stability may beaccomplished in a variety of ways for the purposes of this application.

Isocyanates for use with the polyurethane prepolymer include aliphatic,cycloaliphatic, aromatic aliphatic, aromatic, derivatives thereof, andcombinations of these compounds having two or more isocyanate (NCO)groups per molecule. As briefly mentioned above, however, the isocyanatemay be saturated to improve the light stability of the composition ofthe invention. The isocyanates may be organic polyisocyanate-terminatedprecursors, low free isocyanate precursors, and mixtures thereof. Theisocyanate component may also include any isocyanate-functional monomer,dimer, trimer, or multimeric adduct thereof, precursor, quasi-precursor,or mixtures thereof isocyanate-functional compounds may includemonoisocyanates or polyisocyanates that include any isocyanatefunctionality of two or more.

Suitable isocyanate-containing components include diisocyanates havingthe generic structure: O═C═N—R—N═C═O, where R is preferably a cyclic orlinear or branched hydrocarbon moiety containing from about 1 to 20carbon atoms. The diisocyanate may also contain one or more cyclicgroups. When multiple cyclic groups are present, linear and/or branchedhydrocarbons containing from about 1 to 10 carbon atoms can be presentas spacers between the cyclic groups. In some cases, the cyclic group(s)may be substituted at the 2-, 3-, and/or 4-positions, respectively.Substituted groups may include, but are not limited to, halogens,primary, secondary, or tertiary hydrocarbon groups, or a mixturethereof.

Examples of saturated (aliphatic) diisocyanates that can be used in thepolyurethane precursor include, but are not limited to, ethylenediisocyanate; propylene-1,2-diisocyanate; tetramethylene diisocyanate;tetramethylene-1,4-diisocyanate; 1,6-hexamethylene diisocyanate (HDI);HDI biuret prepared from HDI; octamethylene diisocyanate; decamethylenediisocyanate; 2,2,4-trimethylhexamethylene diisocyanate;2,4,4-trimethylhexamethylene diisocyanate; dodecane-1,12-diisocyanate;cyclobutane-1,3-diisocyanate; cyclohexane-1,2-diisocyanate;cyclohexane-1,3-diisocyanate; cyclohexane-1,4-diisocyanate;methylcyclohexylene diisocyanate (HTDI); 2,4-methylcyclohexanediisocyanate; 2,6-methylcyclohexane diisocyanate; 4,4′-dicyclohexyldiisocyanate; 2,4′-dicyclohexyl diisocyanate; 1,3,5-cyclohexanetriisocyanate; isocyanatomethylcyclohexane isocyanate;1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane;isocyanatoethylcyclohexane isocyanate; bis(isocyanatomethyl)-cyclohexanediisocyanate; 4,4″-bis(isocyanatomethyl)dicyclohexane;2,4′-bis(isocyanatomethyl)dicyclohexane; isophorone diisocyanate (IPDI);triisocyanate of HDI; triisocyanate of 2,2,4-trimethyl-1,6-hexanediisocyanate (TDMI); 4,4′-dicyclohexylmethane diisocyanate (H₁₂MDI);2,4-hexahydrotoluene diisocyanate; 2,6-hexahydrotoluene diisocyanate;aromatic aliphatic isocyanate, such as 1,2-, 1,3-, and 1,4-xylenediisocyanate; meta-tetramethylxylene diisocyanate (m-TMXDI);para-tetramethylxylene diisocyanate (p-TMXDI); trimerized isocyanurateof any polyisocyanate, such as isocyanurate of toluene diisocyanate,trimer of diphenylmethane diisocyanate, trimer of tetramethylxylenediisocyanate, isocyanurate of hexamethylene diisocyanate, isocyanurateof isophorone diisocyanate, and mixtures thereof; dimerized uretdione ofany polyisocyanate, such as uretdione of toluene diisocyanate, uretdioneof hexamethylene diisocyanate, and mixtures thereof; modifiedpolyisocyanate derived from the above isocyanates and polyisocyanates;and mixtures thereof. In one embodiment, the saturated diisocyanatesinclude isophoronediisocyanate (IPDI), 4,4′-dicyclohexylmethanediisocyanate (H₁₂MDI), 1,6-hexamethylene diisocyanate (HDI), or acombination thereof.

As briefly discussed, aromatic aliphatic isocyanates may also be used toform the polyurethane precursor. While use of aromatic aliphaticmaterials does not confer the same amount of light stability to theresultant product compared to those including purely aliphaticmaterials, it does provide a greater degree of light stability to theresultant product compared to those formed with purely aromaticmaterials. Examples of aromatic aliphatic isocyanates include 1,2-,1,3-, and 1,4-xylene diisocyanate; meta-tetramethylxylene diisocyanate(m-TMXDI); para-tetramethylxylene diisocyanate (p-TMXDI); trimerizedisocyanurate of any polyisocyanate, such as isocyanurate of toluenediisocyanate, trimer of diphenylmethane diisocyanate, trimer oftetramethylxylene diisocyanate, isocyanurate of hexamethylenediisocyanate, and mixtures thereof; dimerized uretdione of anypolyisocyanate, such as uretdione of toluene diisocyanate, uretdione ofhexamethylene diisocyanate, and mixtures thereof; a modifiedpolyisocyanate derived from the above isocyanates and polyisocyanates;and mixtures thereof. In addition, the aromatic aliphatic isocyanatesmay be mixed with any of the saturated isocyanates listed above for thepurposes of this invention.

Unsaturated diisocyanates, i.e., aromatic compounds, may also be usedwith the present invention, although the use of unsaturated compounds inthe precursor is preferably coupled with the use of a light stabilizeror pigment as discussed below. Examples of unsaturated diisocyanatesinclude, but are not limited to, substituted and isomeric mixturesincluding 2,2′-, 2,4′-, and 4,4′-diphenylmethane diisocyanate (MDI),3,3′-dimethyl-4,4′-biphenyl diisocyanate (TODI), toluene diisocyanate(TDI), polymeric MDI (PMDI, a brown liquid composed of approximately 50%methylene diisocyanate with the remainder comprised of oligomers ofMDI), carbodimide-modified liquid 4,4′-diphenylmethane diisocyanate,para-phenylene diisocyanate (PPDI), meta-phenylene diisocyanate (MPDI),triphenylmethane-4,4′-, and triphenylmethane-4,4″-triisocyanate,napthylene-1,5,-diisocyanate, 2,4′-, 4,4′-, and 2,2′-biphenyldiisocyanate, polyphenylene polymethylene polyisocyanate (PMDI) (alsoknown as polymeric PMDI), and mixtures thereof.

An isocyanate group reacts with the hydroxyl groups of thehydroxy-terminated component to form a repeating urethane linkage, whichhas the following general structure:

where x is the chain length, i.e., about 1 or greater, and R includesstraight chain or branched hydrocarbon chains having about 1 to about 20carbons, phenyl groups, and mixtures thereof, and R₁ is a straight chainor branched hydrocarbon chain having about 1 to about 20 carbons.

The hydroxy-terminated component suitable for the present invention maybe organic, modified organic, saturated, aliphatic, alicyclic,unsaturated, araliphatic, aromatic, substituted, or unsubstituted innature. The hydroxy-terminated component may be hydroxy-terminatedpolyhydrocarbons including, but not limited to, hydroxy-terminatedpolybutadiene, hydroxy-terminated polyisoprene; poly(hydrogenatedisoprene)polyol; poly(hydrogenated butadiene)polyol; and mixturesthereof.

In particular, the hydroxy-terminated component preferably has two ormore reactive hydrogen groups per molecule, such as primary or secondaryhydroxy groups, and at least one conjugated diene hydrocarbon. Theconjugated diene hydrocarbon may be unsubstituted, 2-substituted, or2,3-disubstituted 1,3-dienes or 4 up to about 12 carbon atoms. In oneembodiment, the diene has up to 6 carbon atoms and the substituents inthe 2- and/or 3-position may be H, alkyl, preferably lower alkyl, aryl,halogen, and mixtures thereof. The diene may be 1,3-butadiene, isoprene,2-cyano-1,3-butadiene, 2,3-dimethyl-1,3,butadiene,2-phenyl-1,3-butadiene, 2-methyl-3-phenyl-1,3-butadiene, and the like.

In one embodiment, the hydroxy-terminated component includeshydroxy-terminated polybutadiene (HTPB) where the functional hydroxygroups are primary hydroxy groups, secondary hydroxy groups, or acombination thereof. The HTPB may have a hydroxyl functionality of about1.8 to about 3 per chain. In one embodiment, the hydroxyl functionalityis about 2 to about 3 per chain. In another embodiment, the hydroxylfunctionality of the HTPB is about 2.2 to about 2.6 per chain. Becausethe hydroxyl functionality has an effect on the viscosity duringprepolymer preparation, in one embodiment, the hydroxyl functionality ofthe HTPB is about 2.0 to about 2.3 per chain. In fact, the use of a HTPBwith lower hydroxyl functionality may alleviate the need for moreisocyanate, which increases cost and handling issues, to reduce theviscosity

Those of ordinary skill in the art would be aware of suitable methods tosynthesize HTPB for use in the present invention. For example, dienemonomers and hydrogen peroxide in a solvent are subjected to freeradical addition polymerization using hydrogen peroxide as the catalyst.As recognized by a skilled artisan, the ratio of cis-1,4 and trans-1,4and 1,2-vinyl unsaturation that occurs in the diene polymers, the numberand location of hydroxyl groups, and the molecular weight of the HTPBmay be a function of the polymerization temperature and the type ofaddition polymerization system employed in forming the polymer.

Further examples of HTPB and methods of preparing HTPB are provided inU.S. Pat. No. 3,652,520, the disclosure of which is incorporated byreference herein. HTPB is also commercially available from Sartomer asPoly Bd® resins, including Poly Bd® R-45HTLO and R-20LM, and Krasol® LBHresins.

When a diisocyanate is reacted with a hydroxy-terminated component ofthe present invention, long polymer chains are formed. A generalreaction scheme between a diisocyanate and a hydroxy-terminatedcomponent having primary hydroxy groups according to the invention is asfollows:

where n is the chain length, i.e., about 1 or greater, and R is astraight chain or branched hydrocarbon chain having about 1 to about 20carbons, a phenyl group, or a mixture thereof.

In addition, when the hydroxy-terminated component includes secondaryhydroxy groups, the reaction scheme is as follows:

where n is the chain length, i.e., about 1 or greater, and R and R₁ areindependently straight chains or branched hydrocarbon chains havingabout 1 to about 20 carbons, a phenyl group, or a mixture thereof.

Furthermore, when the hydroxy-terminated component includes a mixture ofprimary and secondary hydroxy-terminated components, the reaction schemeis as follows:

where n is the chain length, i.e., about 1 or greater, and R and R₁ areindependently straight chains or branched hydrocarbon chains havingabout 1 to about 20 carbons, a phenyl group, or a mixture thereof.

The hydroxy-terminated component may also be blended with otherhydroxyl-terminated components including, but not limited to,hydroxy-terminated polyester, hydroxy-terminated polyether,hydroxy-terminated polycarbonate, hydroxy-terminated polycaprolactones,hydroxy-terminated polyhydrocarbons, hydroxy-terminated acid functionaloligomers or polymers (or ionomers thereof derived from partial or fullneutralization with organic or inorganic cations)

As known to those of ordinary skill in the art, the polyurethaneprepolymer contains some amount of free isocyanate monomer. Thus, in oneembodiment, the polyurethane prepolymer is stripped of free isocyanatemonomer. For example, after stripping, the precursor may contain about 1percent or less free isocyanate monomer. In another embodiment, theprecursor contains about 0.5 percent by weight or less of freeisocyanate monomer.

Polyurea Prepolymer

The prepolymer may also be based on a urea linkages, where theprepolymer is a product formed by a reaction between at least oneisocyanate-containing component and at least one amine-terminatedcomponent. For the purposes of the present invention, the polyureaprepolymers include primarily urea linkages having the following generalstructure:

where x is the chain length, i.e., about 1 or greater, and R includesstraight chain or branched hydrocarbon chains having about 1 to about 20carbons, phenyl groups, and mixtures thereof, and R₁ is a straight chainor branched hydrocarbon chain having about 1 to about 20 carbons.

Because the main difference between the polyurethane prepolymerdiscussed above and the polyurea prepolymer discussed in this section isthe substitution of the hydroxy-terminated component with anamine-terminated component. Therefore, the isocyanates suitable forinclusion in the polyurea prepolymers are the same as those listed abovewith respect to the polyurethane prepolymers, which are incorporated byreference here. And, as above, while saturated isocyanates arepreferred, aromatic aliphatic isocyanates and aromatic isocyanates arecontemplated for use with the present invention.

It should be understood, however, that a prepolymer including primarilyurea linkages may have distinctly different properties than a prepolymerincluding primarily urethane linkages due to the substitution of thehydroxy-terminated component with the amine-terminated component. Forexample, when a polyurea prepolymer is used, the resulting compositionmay have different shear, cut, resiliency, and adhesion properties thana composition with formed from a polyurethane prepolymer.

The amine-terminated component suitable for the present invention may beorganic, modified organic, saturated, aliphatic, alicyclic, unsaturated,araliphatic, aromatic, substituted, or unsubstituted in nature. Themolecular weight of the amine-terminated component for use in theinvention may range from about 100 to about 10,000. In one embodiment,the amine-terminated component is about 500 or greater, preferably about1000 or greater, and even more preferably about 2000 or greater. Inanother embodiment, the amine-terminated component molecular weight isabout 8000 or less, preferably about 4,000 or less, and more preferablyabout 3,000 or less. For example, in one embodiment, the molecularweight of the amine-terminated component is about 1000 to about 4000.Because lower molecular weight amine-terminated components may be proneto forming solid polyureas, a higher molecular weight oligomer may beused to avoid solid formation.

The amine-terminated component may be amine-terminated polyhydrocarbonsincluding, but not limited to, amine-terminated polybutadiene,amine-terminated polyisoprene; poly(hydrogenated isoprene)amine;poly(hydrogenated butadiene)amine; and mixtures thereof. In particular,the hydroxy-terminated component preferably has two or more reactiveamino groups per molecule, such as primary or secondary amino groups,and at least one conjugated diene hydrocarbon. The conjugated dienehydrocarbon may be unsubstituted, 2-substituted, or 2,3-disubstituted1,3-dienes or 4 up to about 12 carbon atoms. In one embodiment, thediene has up to 6 carbon atoms and the substituents in the 2- and/or3-position may be H, alkyl, preferably lower alkyl, aryl, halogen, andmixtures thereof. The diene may be 1,3-butadiene, isoprene,2-cyano-1,3-butadiene, 2,3-dimethyl-1,3,butadiene,2-phenyl-1,3-butadiene, 2-methyl-3-phenyl-1,3-butadiene, and the like.

In one embodiment, the amine-terminated component includesamine-terminated polybutadiene (ATPB) where the functional amino groupsare primary amino groups, secondary amino groups, or a combinationthereof. The ATPB may have amino functionality of about 1.8 to about 3per chain. In one embodiment, the amino functionality is about 2 toabout 3 per chain. In another embodiment, the amino functionality of theATPB is about 2.2 to about 2.6 per chain. Because the aminofunctionality has an effect on the viscosity during prepolymerpreparation, in one embodiment, the amino functionality of the ATPB isabout 2.0 to about 2.3 per chain. In fact, the use of a ATPB with loweramino functionality may alleviate the need for more isocyanate, whichincreases cost and handling issues, to reduce the viscosity.

Those of ordinary skill in the art would be aware of methods to prepareamine-terminated polybutadienes for use with the present invention. Forexample, ATPBs may be synthesized from functionalized initiators andbutadiene monomer or by converting hydroxyl-terminated polybutadiene(HTPB) to ATPB by multi-step synthetic pathways. U.S. Pat. No.4,658,062, the entire disclosure of which is incorporated by referenceherein, discusses such methods. In addition, U.S. Pat. No. 4,994,621discloses reacting liquid HTPB polymer with several oxirane units perhydroxyl group, to produce a secondary hydroxyl-terminated polymercontaining ether linkages, which are then aminated by reacting ammoniawith the hydroxyl groups under reducing conditions provided by hydrogenunder pressure. Furthermore, ATPBs having one or two terminal aminogroups may be prepared by cyanoalkylating a hydroxy-terminatedpolybutadiene by Michael addition of acrylonitrile in the presence of abase, forming nitrile termination, followed by hydrogenation in thepresence of a Group VIII metal as catalyst. U.S. Pat. No. 6,831,136, thedisclosure of which is incorporated by reference herein in its entirety,discusses such a method.

When a diisocyanate is reacted with an amine-terminated component of thepresent invention, long polymer chains are formed. A general reactionscheme between a diisocyanate and a amine-terminated component havingprimary amino groups according to the invention is as follows:

where n is the chain length, i.e., about 1 or greater, and R and R₁ areindependently straight chains or branched hydrocarbon chains havingabout 1 to about 20 carbons, a phenyl group, or a mixture thereof.

In addition, when the amine-terminated component includes secondaryamino groups, the reaction scheme is as follows:

where n is the chain length, i.e., about 1 or greater, and R and R₁ areindependently straight chains or branched hydrocarbon chains havingabout 1 to about 20 carbons, a phenyl group, or a mixture thereof.

Furthermore, when the amine-terminated component includes a mixture ofprimary and secondary amine-terminated components, the reaction schemeis as follows:

where n is the chain length, i.e., about 1 or greater, and R and R₁ areindependently straight chains or branched hydrocarbon chains havingabout 1 to about 20 carbons, a phenyl group, or a mixture thereof.

The amine-terminated component may be blended with otheramine-terminated components including, but not limited to,amine-terminated hydrocarbons, amine-terminated polyethers,amine-terminated polyesters, amine-terminated polycarbonates,amine-terminated polycaprolactones, and mixtures thereof.

Hybrid Prepolymer

The prepolymer may also have both urethane and urea linkages. Such aprepolymer is distinct from a polyurethane prepolymer including only anisocyanate and a hydroxy-terminated component or a polyurea prepolymerincluding only an isocyanate and an amine-terminated component. For thesake of clarity, this type of segment will be referred to as a hybridprepolymer throughout the application.

For example, in one embodiment, the isocyanate-reactive component may behave at least one terminal hydroxyl group and at least one terminalamino group. In particular, the isocyanate-reactive component may haveat least one conjugated diene hydrocarbon terminated at one end with aprimary or secondary amino group and terminated at the other end with aprimary or secondary hydroxyl group.

In this regard, the hybrid isocyanate-reactive component may have one ofthe following general formulas:

R, R₁, and R₂ may independently be any alkyl group having from about 1to about 20 carbon atoms, preferably about 1 to about 12 carbon atoms, aphenyl group, a cyclic group, or mixture thereof. X may beunsubstituted, 2-substituted, or 2,3-disubstituted 1,3-dienes or 4 up toabout 12 carbon atoms and n is the chain length, i.e., about 1 orgreater. In one embodiment, the diene has up to 6 carbon atoms and thesubstituents in the 2- and/or 3-position may be H, alkyl, preferablylower alkyl, aryl, halogen, and mixtures thereof. The diene may be1,3-butadiene, isoprene, 2-cyano-1,3-butadiene,2,3-dimethyl-1,3,butadiene, 2-phenyl-1,3-butadiene,2-methyl-3-phenyl-1,3-butadiene, and the like.

When a diisocyanate is reacted with a hybrid isocyanate-reactivecomponent of the present invention, long polymer chains are formed. Ageneral reaction scheme between a diisocyanate and a hybridisocyanate-reactive component having primary hydroxy and amino groupsaccording to the invention is as follows:

where n is the chain length, i.e., about 1 or greater, and R and R₁ areindependently straight chains or branched hydrocarbon chains havingabout 1 to about 20 carbons, a phenyl group, or a mixture thereof.

In addition, when the hybrid isocyanate-reactive component includes asecondary hydroxy group and a primary amino group, the reaction schemeis as follows:

where n is the chain length, i.e., about 1 or greater, and R and R₁ areindependently straight chains or branched hydrocarbon chains havingabout 1 to about 20 carbons, a phenyl group, or a mixture thereof.

Furthermore, when the hybrid isocyanate-reactive component includes aprimary hydroxy group and a secondary amino group, the reaction schemeis as follows:

where n is the chain length, i.e., about 1 or greater, and R and R₂ areindependently straight chains or branched hydrocarbon chains havingabout 1 to about 20 carbons, a phenyl group, or a mixture thereof.

Moreover, when the hybrid isocyanate-reactive component includessecondary hydroxyl and amino groups, the reaction scheme is as follows:

where n is the chain length, i.e., about 1 or greater, and R, R₁, and R₂are independently straight chains or branched hydrocarbon chains havingabout 1 to about 20 carbons, a phenyl group, or a mixture thereof.Curatives

The prepolymers discussed above may be cured in several ways. In oneembodiment, the curing process involves the reaction of the prepolymerwith an amine-terminated curing agent, a hydroxy-terminated curingagent, or a mixture thereof. The use of such curing agents promotescrosslinking of the hard segments, i.e., the isocyanate groups and theamino and/or hydroxyl groups.

The amine-terminated and/or hydroxy-terminated curing agent(s) may bepresent in a curative blend with a free radical initiator, such as anorganic peroxide to, which crosslinks the soft segments of theprepolymer, i.e., the unsaturated portion of the elastomer. For example,the curative blend is added to the prepolymer and the temperature iselevated such that the soft and hard segments are crosslinked.

Amine-Terminated Curing Agent

The prepolymers of the invention be cured with a single amine-terminatedcuring agent or a mixture of amine-terminated curing agents. Suitableamine-terminated curing agents include, but are not limited to, ethylenediamine; hexamethylene diamine; 1-methyl-2,6-cyclohexyl diamine; 2,2,4-and 2,4,4-trimethyl-1,6-hexanediamine;4,4′-bis-(sec-butylamino)-dicyclohexylmethane and derivatives thereof;1,4-bis-(sec-butylamino)-cyclohexane;1,2-bis-(sec-butylamino)-cyclohexane; 4,4′-dicyclohexylmethane diamine;1,4-cyclohexane-bis-(methylamine); 1,3-cyclohexane-bis-(methylamine),isomers, and mixtures thereof; diethylene glycol bis-(aminopropyl)ether;2-methylpentamethylene-diamine; diaminocyclohexane, isomers, andmixtures thereof; diethylene triamine; triethylene tetramine;tetraethylene pentamine; propylene diamine; 1,3-diaminopropane;dimethylamino propylamine; diethylamino propylamine;imido-bis-(propylamine); monoethanolamine, diethanolamine;triethanolamine; monoisopropanolamine, diisopropanolamine;isophoronediamine; 4,4′-methylenebis-(2-chloroaniline);3,5-dimethylthio-2,4-toluenediamine;3,5-dimethylthio-2,6-toluenediamine; 3,5-diethylthio-2,4-toluenediamine;3,5-diethylthio-2,6-toluenediamine; 4,4′-bis-(sec-butylamino)-benzene;and derivatives thereof; 1,4-bis-(sec-butylamino)-benzene;1,2-bis-(sec-butylamino)-benzene; N,N′-dialkylamino-diphenylmethane;trimethyleneglycol-di-p-aminobenzoate;polytetramethyleneoxide-di-p-aminobenzoate;4,4′-methylenebis-(3-chloro-2,6-diethyleneaniline);4,4′-methylenebis-(2,6-diethylaniline); meta-phenylenediamine;paraphenylenediamine; N,N′-diisopropyl-isophoronediamine;polyoxypropylene diamine; propylene oxide-based triamine;3,3′-dimethyl-4,4′-diaminocyclohexylmethane; and mixtures thereof. Inone embodiment, the amine-terminated curing agent is4,4′-bis-(sec-butylamino)-dicyclohexylmethane.

The amine-terminated curing agent may have a molecular weight of about64 or greater. In one embodiment, the molecular weight of theamine-curing agent is about 2000 or less. In addition, any of theamine-terminated moieties listed above for use as theisocyanate-reactive component to form the prepolymer may be used ascuring agents to react with the prepolymers.

Of the list above, the saturated amine-terminated curing agents suitablefor use with the present invention include, but are not limited to,ethylene diamine; hexamethylene diamine; 1-methyl-2,6-cyclohexyldiamine; 2,2,4- and 2,4,4-trimethyl-1,6-hexanediamine;4,4′-bis-(sec-butylamino)-dicyclohexylmethane;1,4-bis-(sec-butylamino)-cyclohexane;1,2-bis-(sec-butylamino-cyclohexane; derivatives of4,4′-bis-(sec-butylamino)-dicylohexylmethane; 4,4′-dicyclohexylmethanediamine; 1,4-cyclohexane-bis-(methylamine);1,3-cyclohexane-bis-(methylamine); diethylene glycolbis-(aminopropyl)ether; 2-methylpentamethylene-diamine;diaminocyclohexane; diethylene triamine; triethylene tetramine;tetraethylene pentamine; propylene diamine; dipropylene triamine;1,3-diaminopropane; dimethylamino propylamine; diethylamino propylamine;imido-bis-(propylamine); monoethanolamine, diethanolamine;triethanolamine; monoisopropanolamine, diisopropanolamine;triisopropanolamine; isophoronediamine; N,N′-diisopropylisophoronediamine and mixtures thereof.

In one embodiment, the curative used with the prepolymer include3,5-dimethylthio-2,4-toluenediamine,3,5-dimethyl-thio-2,6-toluenediamine,4,4′-bis-(sec-butylamino)-diphenylmethane, N,N′-diisopropyl-isophoronediamine; polyoxypropylene diamine; propylene oxide-based triamine;3,3′-dimethyl-4,4′-diaminocyclohexylmethane; and mixtures thereof.

Because unhindered primary diamines result in a rapid reaction betweenthe isocyanate groups and the amine groups, in certain instances, ahindered secondary diamine may be more suitable for use in theprepolymer. Without being bound to any particular theory, it is believedthat an amine with a high level of stearic hindrance, e.g., a tertiarybutyl group on the nitrogen atom, has a slower reaction rate than anamine with no hindrance or a low level of hindrance. For example,4,4′-bis-(sec-butylamino)-dicyclohexylmethane (Clearlink 1000) may besuitable for use in combination with an isocyanate to form the polyureaprepolymer. In addition, N,N′-diisopropyl-isophorone diamine, availablefrom Huntsman Corporation under the tradename Jefflink, may be used asthe secondary diamine curing agent.

In addition, a trifunctional curing agent can be used to help improvecross-linking and, thus, to further improve the shear resistance of theresulting polyurea elastomers. In one embodiment, a triol such astrimethylolpropane or a tetraol such as N,N,N′,N′-tetrakis(2-hydroxylpropyl)ethylenediamine may be added to the formulations.

Hydroxy-Terminated Curing Agent

The prepolymers of the invention may also be cured with a singlehydroxy-terminated curing agent or a mixture of hydroxy-terminatedcuring agents. Suitable hydroxy-terminated curing agents include, butare not limited to, ethylene glycol; diethylene glycol; polyethyleneglycol; propylene glycol; 2-methyl-1,3-propanediol;2,-methyl-1,4-butanediol; dipropylene glycol; polypropylene glycol;1,2-butanediol; 1,3-butanediol; 1,4-butanediol; 2,3-butanediol;2,3-dimethyl-2,3-butanediol; trimethylolpropane; cyclohexyldimethylol;triisopropanolamine; N,N,N′N′-tetra-(2-hydroxypropyl)-ethylene diamine;diethylene glycol bis-(aminopropyl)ether; 1,5-pentanediol;1,6-hexanediol; 1,3-bis-(2-hydroxyethoxy)cyclohexane;1,4-cyclohexyldimethylol;1,3-bis-[2-(2-hydroxyethoxy)ethoxy]cyclohexane;1,3-bis-{2-[2-(2-hydroxyethoxy)ethoxy]ethoxy}cyclohexane;polytetramethylene ether glycol, preferably having a molecular weightranging from about 250 to about 3900;resorcinol-di-(beta-hydroxyethyl)ether and its derivatives;hydroquinone-di-(beta-hydroxyethyl)ether and its derivatives;1,3-bis-(2-hydroxyethoxy)benzene;1,3-bis-[2-(2-hydroxyethoxy)ethoxy]benzene;1,3-bis-{2-[2-(2-hydroxyethoxy)ethoxy]ethoxy}benzene;N,N-bis(.beta.-hydroxypropyl)aniline; 2-propanol-1,1′-phenylaminobis;and mixtures thereof.

The hydroxy-terminated curing agent may have a molecular weight of atleast about 50. In one embodiment, the molecular weight of thehydroxy-terminated curing agent is about 2000 or less. In yet anotherembodiment, the hydroxy-terminated curing agent has a molecular weightof about 250 to about 3900. It should be understood that molecularweight, as used herein, is the absolute weight average molecular weightand would be understood as such by one of ordinary skill in the art.

The saturated hydroxy-terminated curing agents, included in the listabove, are preferred when making a light stable composition. Thosesaturated hydroxy-terminated curing agents include, but are not limitedto, ethylene glycol; diethylene glycol; polyethylene glycol; propyleneglycol; 2-methyl-1,3-propanediol; 2,-methyl-1,4-butanediol; dipropyleneglycol; polypropylene glycol; 1,2-butanediol; 1,3-butanediol;1,4-butanediol; 2,3-butanediol; 2,3-dimethyl-2,3-butanediol;trimethylolpropane; cyclohexyldimethylol; triisopropanolamine;N,N,N′,N′-tetra-(2-hydroxypropyl)-ethylene diamine; diethylene glycolbis-(aminopropyl)ether, 1,5-pentanediol; 1,6-hexanediol;1,3-bis-(2-hydroxyethoxy)cyclohexane; 1,4-cyclohexyldimethylol;1,3-bis-[2-(2-hydroxy ethoxy)ethoxy]cyclohexane;1,3-bis-(2-[2-(2-hydroxyethoxy)ethoxy]ethoxy)cyclohexane;polytetramethylene ether glycol having molecular weight ranging fromabout 250 to about 3900; and mixtures thereof.

Free Radical Initiator

The free radical initiator promotes crosslinking of the unsaturatedsegments of the prepolymer, i.e., the conjugated diene hydrocarbon. Inone embodiment, the free radical initiator includes a peroxide. Theperoxide is not specifically limited, however, suitable peroxides foruse in the vulcanization process include, but are not limited to, thefollowing:

and mixtures thereof. In addition, di-t-amyl peroxide,1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane or1,1-di(t-butylperoxy) 3,3,5-trimethyl cyclohexane, di-t-butyl peroxide,2,5-di-(t-butylperoxy)-2,5-dimethyl hexane,2,5-dimethyl-2,5-di-benzoylperoxyhexane,n-butyl-4,4-bis(t-butylperoxy)valerate, lauryl peroxide, benzoylperoxide, t-butyl hydroperoxide, t-butyl cumylperoxide, t-butylperoxybenzoate, 2,4-dichloro-benzoyl peroxide, and mixtures thereof arecontemplated for use in curing the unsaturated soft segments in theprepolymer.

It is well known that peroxides are available in a variety of formshaving different activity. The activity is typically defined by the“active oxygen content.” For example, DI-CUP® 40C, commerciallyavailable from GEO Specialty Chemicals of Gibbstown, N.J., is 40 percentactive. The peroxide is typically present in an amount greater thanabout 0.1 parts per hundred of the composition, preferably about 0.1 to15 parts per hundred of the composition, and more preferably about 0.2to 5 parts per hundred of the composition. If the peroxide is present inpure form, it is preferably present in an amount of at least about 0.25pph, more preferably between about 0.35 pph and about 2.5 pph, and mostpreferably between about 0.5 pph and about 2 pph per hundred of thecomposition. Peroxides are also available in concentrate form, which arewell-known to have differing activities, as described above. In thiscase, if concentrate peroxides are employed in the present invention,one skilled in the art would know that the concentrations suitable forpure peroxides are easily adjusted for concentrate peroxides by dividingby the activity. For example, 2 pph of a pure peroxide is equivalent 4pph of a concentrate peroxide that is 50 percent active (i.e., 2 dividedby 0.5=4).

In addition to peroxides, other free radical sources suitable for usewith the present invention include persulfates, azo compounds,benzophenones, hydrazides, and combinations thereof are contemplated foruse as part of the cure system for the dipolymer. In this aspect of theinvention, the amount of free radical source is about 5 pph or less,preferably about 3 pph or less, more preferably about 2.5 pph or less,and even more preferably about 2 pph or less per hundred of thecomposition. In still another embodiment, the amount of free radicalsource is about 1 pph or less, preferably about 0.75 pph or less perhundred of the composition.

Curative Blends

The amine-terminated and hydroxy-terminated curing agents may be presentin a blend with the free radical initiator. For example, in oneembodiment, the curative blend includes at least one amine-terminatedcuring agent and a free radical initiator. In another embodiment, thecurative blend is a mixture of at least one hydroxy-terminated curingagent and a free radical initiator. In yet another embodiment, thecurative blend includes at least one hydroxy-terminated curing agent, atleast one amine-terminated curing agent, and a free radical initiator.

Furthermore, the curative blend may include a freezing point depressingagent to slow the onset of solidification. Examples of freezing pointdepressing agents suitable for use in this aspect of the invention aredisclosed in U.S. Patent Publication No. 2003/0212240, which isincorporated by reference herein in its entirety. In one embodiment, thefreezing point depressing agent includes, but is not limited to,ethylene diamine, 1,3-diaminopropane, dimethylamino propylamine,tetraethylene pentamine, 1,2-propylenediamine, diethylaminopropylamine,2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine,and mixtures thereof.

Forming the Compositions of the Invention

There are two basic techniques used to process the compositions of theinvention: the one-shot technique and the prepolymer technique. Theone-shot technique reacts the isocyanate-containing component and theisocyanate-reactive component, and the curing agent or curative blend inone step, whereas the prepolymer technique requires a first reactionbetween the isocyanate-reactive component(s) and an isocyanate toproduce the prepolymer, and a subsequent reaction between the prepolymerand a curing agent or curative blend. Either method may be employed toproduce the compositions of the invention, however, the prepolymertechnique is preferred because it provides better control of chemicalreaction and, consequently, results in more uniform properties for theelastomers.

In particular, whether the curative is a single amine-terminated curingagent and/or hydroxy-terminated curing agent, a mixture ofamine-terminated curing agent(s) and/or hydroxy-terminated curingagent(s), or a blend of amine-terminated curing agent(s) and/orhydroxy-terminated curing agent(s) and a free radical initiator, oncereacted with the prepolymer, the isocyanate (NCO) groups react with thehydroxyl or amino groups to crosslink the prepolymer.

For example, when a urethane prepolymer reacts with a curing agent orcurative blend including hydroxy-terminated components, the resultingpolymer includes urethane linkages, as shown in the following generalreaction scheme:

where n is the chain length, i.e., about 1 or greater, X is a curingagent or curative blend including hydroxy groups, R and R₂ areindependently straight chains or branched hydrocarbon chains havingabout 1 to about 20 carbons, a phenyl group, or a mixture thereof.

When a urea prepolymer reacts with a curing agent or curative blendincluding amine-terminated components, the resulting polymer includesurea linkages, as shown in the following general reaction scheme:

where n is the chain length, i.e., about 1 or greater, X is a curingagent or curative blend including amino groups, R and R₂ areindependently straight chains or branched hydrocarbon chains havingabout 1 to about 20 carbons, a phenyl group, or a mixture thereof.

When a hybrid prepolymer reacts with a curing agent or curative blendincluding hydroxy-terminated or amine-terminated components, theresulting polymer includes urea and urethane linkages, as shown in thefollowing general reaction scheme:

where n is the chain length, i.e., about 1 or greater, X is a curingagent or curative blend including hydroxy groups, amino groups, orcombinations thereof, R and R₂ are independently straight chains orbranched hydrocarbon chains having about 1 to about 20 carbons, a phenylgroup, or a mixture thereof.

Those of ordinary skill in the art would be aware of the similar generalreaction schemes relating to the reaction between a urethane prepolymerand a curing agent or curative blend including amino groups and a ureaprepolymer and a curing agent or curative blend including hydroxygroups. As discussed above, similar to a polymer resulting from the useof a hybrid prepolymer, the resulting polymer in these reactions willalso include both urethane and urea linkages.

When the curative blend includes a free radical initiator, both the softand hard segments of the polymer are crosslinked. In on embodiment, theprepolymer and curative blend are mixed and poured into a mold. Thetemperature of the mold preferably ranges from about 100° F. to about250° F. In one embodiment, the mold temperature ranges from about 120°F. to about 200° F. In another embodiment, the temperature of the moldranges from about 140° F. to about 180° F. In still another embodiment,the mold temperature is about 150° F. to about 170° F. After a period oftime, the mold temperature is elevated to initiate the free radical. Inone embodiment, the period of time prior to elevation ranges from about1 minute to about 30 minutes. In another embodiment, the period of timeprior to elevation ranges from about 5 minutes to about 20 minutes,preferably about 8 minutes to about 15 minutes. After elevation, thematerial may be allowed to cure for an additional period of time rangingfrom about 5 minutes to about 25 minutes, preferably about 8 minutes toabout 20 minutes, and even more preferably about 12 minutes to about 18minutes.

The elevation temperature may be any temperature that initiates the freeradical. For example, the elevation temperature may range from about250° F. to about 400° F. In one embodiment, the elevation temperaturemay range from about 275° F. to about 350° F. In another embodiment, theelevation temperature ranges from about 300° F. to about 330° F.

The reaction scheme between a polyurethane prepolymer and a curativeblend including hydroxy groups and a free radical initiator, such as anorganic peroxide, is as follows:

where n is the chain length, i.e., about 1 or greater, XP is a curativeblend including hydroxy groups and an organic peroxide, R and R₂ areindependently straight chains or branched hydrocarbon chains havingabout 1 to about 20 carbons, a phenyl group, or a mixture thereof.

When a urea prepolymer reacts with a curing agent or curative blendincluding amino groups and a free radical initiator, such as an organicperoxide, the resulting polymer includes urea linkages, as shown in thefollowing general reaction scheme:

where n is the chain length, i.e., about 1 or greater, XP is a curativeblend including amino groups and an organic peroxide, R and R₂ areindependently straight chains or branched hydrocarbon chains havingabout 1 to about 20 carbons, a phenyl group, or a mixture thereof.

When a hybrid prepolymer reacts with a curing agent or curative blendincluding hydroxy-terminated or amine-terminated components, theresulting polymer includes urea and urethane linkages, as shown in thefollowing general reaction scheme:

where n is the chain length, i.e., about 1 or greater, XP is a curativeblend including hydroxy groups, amino groups, or combinations thereof,and an organic peroxide, R and R₂ are independently straight chains orbranched hydrocarbon chains having about 1 to about 20 carbons, a phenylgroup, or a mixture thereof.Blends

The compositions of the present invention may also be blended with otherpolymers. In particular, the compositions of the invention preferablyinclude about 1 percent to about 100 percent of the crosslinkedpolyurethane/polyurea. In one embodiment, the compositions contain about10 percent to about 90 percent of the crosslinked polyurethane/polyurea,preferably from about 10 percent to about 75 percent of the crosslinkedpolyurethane/polyurea, and about 90 percent to 10 percent, morepreferably from about 90 percent to about 25 percent of the secondpolymer component and/or other materials as described below. Forexample, a blend in accordance in the present invention may have about10 percent to about 40 percent of the crosslinked polyurethane/polyureaand about 60 percent to about 90 percent of another thermoplasticpolymer, e.g., a conventional ionomer. In an alternate embodiment, ablend in accordance with the invention may include about 40 percent toabout 80 percent of the crosslinked polyurethane/polyurea and about 20percent to about 60 percent of another thermoplastic polymer. Unlessotherwise stated herein, all percentages are given in percent by weightof the total composition of the golf ball layer in question.

For example, the compositions of the invention may be present in a blendwith ionomeric copolymers or terpolymers, ionomeric precursors,thermoplastics, polyamides, polycarbonates, polyesters, polyurethanes,polyureas, thermoplastic elastomers, polybutadiene rubber, balata,grafted and non-grafted metallocene-catalyzed polymers, single-sitepolymers, high-crystalline acid polymers, cationic polymers, cationicand anionic urethane ionomers and urethane epoxies, polyurethaneionomers, polyurea ionomers, epoxy resins, polyethylenes, polyacrylin,siloxanes, and mixtures thereof.

Examples of suitable urethane ionomers are disclosed in U.S. Pat. No.5,692,974, the disclosure of which is hereby incorporated by referencein its entirety. Other examples of suitable polyurethanes are describedin U.S. Pat. No. 5,334,673, the entire disclosure of which isincorporated by reference herein. Examples of suitable polyureas used toform the polyurea ionomer listed above are discussed in U.S. Pat. No.5,484,870. In particular, the polyureas of U.S. Pat. No. 5,484,870 areprepared by reacting a polyisocyanate and a polyamine curing agent toyield polyurea, which are distinct from the polyureas of the presentinvention that are formed from a polyurea prepolymer and curing agent.Examples of suitable polyurethanes cured with epoxy group containingcuring agents are disclosed in U.S. Pat. No. 5,908,358. The disclosuresof the above patents are incorporated herein by reference in theirentirety.

One of ordinary skill in the art would be well aware of methods to blendthese polymeric materials with the organically modified silicate of theinvention to form a composition for use in golf ball layers.

Additives

The compositions of the invention may include a variety of additives.For example, the compositions of the invention may be foamed by theaddition of the at least one physical or chemical blowing or foamingagent. The use of a foamed polymer allows the golf ball designer toadjust the density or mass distribution of the ball to adjust theangular moment of inertia, and, thus, the spin rate and performance ofthe ball. Foamed materials also offer a potential cost savings due tothe reduced use of polymeric material.

Blowing or foaming agents useful include, but are not limited to,organic blowing agents, such as azobisformamide; azobisisobutyronitrile;diazoaminobenzene; N,N-dimethyl-N,N-dinitroso terephthalamide;N,N-dinitrosopentamethylene-tetramine; benzenesulfonyl-hydrazide;benzene-1,3-disulfonyl hydrazide; diphenylsulfon-3-3, disulfonylhydrazide; 4,4′-oxybis benzene sulfonyl hydrazide; p-toluene sulfonylsemicarbizide; barium azodicarboxylate; butylamine nitrile; nitroureas;trihydrazino triazine; phenyl-methyl-uranthan; p-sulfonhydrazide;peroxides; and inorganic blowing agents such as ammonium bicarbonate andsodium bicarbonate. A gas, such as air, nitrogen, carbon dioxide, etc.,can also be injected into the composition during the injection moldingprocess.

Additionally, a foamed composition of the present invention may beformed by blending microspheres with the composition either during orbefore the molding process. Polymeric, ceramic, metal, and glassmicrospheres are useful in the invention, and may be solid or hollow andfilled or unfilled. In particular, microspheres up to about 1000micrometers in diameter are useful. Furthermore, the use of liquidnitrogen for foaming, as disclosed in U.S. Pat. No. 6,386,992, which isincorporated by reference herein, may produce highly uniform foamedcompositions for use in the present invention.

Fillers may also be added to the compositions of the invention to affectrheological and mixing properties, the specific gravity (i.e.,density-modifying fillers), the modulus, the tear strength,reinforcement, and the like. The fillers are generally inorganic, andsuitable fillers include numerous metals, metal oxides and salts, suchas zinc oxide and tin oxide, as well as barium sulfate, zinc sulfate,calcium carbonate, zinc carbonate, barium carbonate, clay, tungsten,tungsten carbide, an array of silicas, regrind (recycled core materialtypically ground to about 30 mesh particle), high-Mooney-viscosityrubber regrind, and mixtures thereof.

For example, the compositions of the invention can be reinforced byblending with a wide range of density-adjusting fillers, e.g., ceramics,glass spheres (solid or hollow, and filled or unfilled), and fibers,inorganic particles, and metal particles, such as metal flakes, metallicpowders, oxides, and derivatives thereof, as is known to those withskill in the art. The selection of such filler(s) is dependent upon thetype of golf ball desired, i.e., one-piece, two-piece, multi-component,or wound, as will be more fully detailed below. Generally, the fillerwill be inorganic, having a density of greater than 4 g/cc, and will bepresent in amounts between about 5 and about 65 weight percent based onthe total weight of the polymer components included in the layer(s) inquestion. Examples of useful fillers include zinc oxide, barium sulfate,calcium oxide, calcium carbonate, and silica, as well as other knowncorresponding salts and oxides thereof.

When the compositions of the invention are used in the core layers ofthe golf ball, fillers may also be used to modify the weight of the coreto create a specialty ball, e.g., a lower weight ball is preferred for aplayer having a low swing speed.

Additional materials conventionally included in other golf ballcompositions may also be included in the compositions of the invention.For example, antioxidants, stabilizers, softening agents, plasticizers,including internal and external plasticizers, reinforcing materials, andcompatibilizers may also be added to any composition of the invention.Those of ordinary skill in the art are aware of the purpose of theseadditives and the amounts that should be employed to fulfill thosepurposes.

Golf Ball Construction

As discussed briefly above, the compositions of the present inventionmay be used with any type of ball construction including, but notlimited to, one-piece, two-piece, three-piece, and four-piece designs, adouble core, a double cover, an intermediate layer(s), a multilayercore, and/or a multi-layer cover depending on the type of performancedesired of the ball. That is, the compositions of the invention may beused in a core, an intermediate layer, and/or a cover of a golf ball,each of which may have a single layer or multiple layers.

As used herein, the term “multilayer” means at least two layers. Forinstance, the core may be a one-piece core or a multilayer core, i.e., acore that has an innermost component with an additional core layer oradditional core layers disposed thereon. As used herein, the terms“core” and “center” are generally used interchangeably to reference theinnermost component of the ball. In some embodiments, however, the term“center” is used when there are multiple core layers, i.e., a center andan outer core layer.

When the golf ball of the present invention includes an intermediatelayer, which may also include more than one layer, this layer may beincorporated with a single or multilayer cover, a single or multi-piececore, with both a single layer cover and core, or with both a multilayercover and a multilayer core. The intermediate layer may be also bereferred to as an inner cover layer or outer core layer, or any otherlayer(s) disposed between the inner core and the outer cover of a golfball.

Referring to FIG. 1, a golf ball 2 of the present invention can includea center 4 and a cover 6 surrounding the center 4. While dimensions andmaterials are discussed in more detail below, a golf ball of theinvention can include a large core, e.g., about 1.55 inches to about1.60 inches, and a relatively soft, thin cover formed from thecomposition of the invention.

Referring to FIG. 2, a golf ball 8 of the present invention can includea center 10, a cover 14, and at least one intermediate layer 12 disposedbetween the cover and the center. In one embodiment, the intermediatelayer 12 is formed from the composition of the invention. In anotherembodiment, the cover 14 is formed from the composition of theinvention. Each of the cover and center layers in FIG. 1 or 2 mayinclude more than one layer, i.e., the golf ball can be a conventionalthree-piece wound ball, a two-piece ball, a ball having a multi-layercore and an intermediate layer or layers, etc.

Also, FIG. 3 shows a golf ball 16 of the present invention including alarge core 18, a cover 22, and an inner cover layer 20. In oneembodiment, the core 18 includes a center and an outer core layer. Theinner cover layer 20 and/or cover 22 may be formed from the compositionof the invention. In one embodiment, the inner cover layer 20 is formedfrom the composition of the invention and the cover 22 is formed from apolyurethane or polyurea material.

In another embodiment, as shown in FIG. 4, a golf ball 24 of the presentinvention can include a large core having a center 26 and anintermediate layer 28 disposed underneath a dual cover having an innercover layer 30 and an outer cover layer 32. The inner cover layer 30and/or outer cover layer 32 is formed from the compositions of theinvention. Further, any of the figures detailed herein may includeembodiments wherein an optional wound layer is disposed between thecenter and the core of the golf ball.

Other non-limiting examples of suitable types of ball constructions thatmay be used with the present invention include those described in U.S.Pat. Nos. 6,056,842, 5,688,191, 5,713,801, 5,803,831, 5,885,172,5,919,100, 5,965,669, 5,981,654, 5,981,658, and 6,149,535, as well as inPublication Nos. US2001/0009310 A1, US2002/0025862, and US2002/0028885.The entire disclosures of these patents and published patentapplications are incorporated by reference herein.

Golf Ball Core Layer(s)

The cores of the golf balls formed according to the invention may besolid, semi-solid, hollow, fluid-filled or powder-filled, one-piece ormulti-component cores. As used herein, the term “fluid” includes aliquid, a paste, a gel, a gas, or any combination thereof; the term“fluid-filled” includes hollow centers or cores; and the term“semi-solid” refers to a paste, a gel, or the like.

The core may have a diameter of about 1.5 inches to about 1.62 inchesand the cover layer thickness may range from about 0.03 inches to about0.06 inches. The core compression preferably ranges from about 30 toabout 120 atti and the overall ball compression is about 50 to about110.

Any core material known to one of ordinary skill in that art is suitablefor use in the golf balls of the invention. Suitable core materialsinclude thermoset materials, such as rubber, styrene butadiene,polybutadiene, isoprene, polyisoprene, trans-isoprene, as well asthermoplastics such as ionomer resins, polyamides or polyesters, andthermoplastic and thermoset polyurethane elastomers. For example,butadiene rubber, which, in an uncured state, typically has a Mooneyviscosity (measured according to ASTM D1646-99) greater than about 20,preferably greater than about 30, and more preferably greater than about40, may be used in one or more core layers of the golf balls preparedaccording to the present invention. In addition, the compositions of theinvention may be incorporated the core.

A free-radical source, often alternatively referred to as a free-radicalinitiator, may optionally be used in the core, or one or more layers ofthe golf balls according to the invention, particularly when a polymercomponent includes a thermoset material. The free radical source for ispreferably a peroxide, more preferably an organic peroxide. The peroxideis typically present in an amount greater than about 0.1 parts perhundred of the total polymer component, preferably about 0.1 to 15 partsper hundred of the polymer component, and more preferably about 0.2 to 5parts per hundred of the total polymer component. It should beunderstood by those of ordinary skill in the art that the presence ofcertain components may require a larger amount of free-radical sourcethan the amounts described herein. The free radical source mayalternatively or additionally be one or more of an electron beam, UV orgamma radiation, x-rays, or any other high energy radiation sourcecapable of generating free radicals. It should be further understoodthat heat often facilitates initiation of the generation of freeradicals when peroxides are used as a free-radical initiator.

Golf Ball Intermediate Layer(s)

When the golf ball of the present invention includes an intermediatelayer, such as an inner cover layer or outer core layer, i.e., anylayer(s) disposed between the inner core and the outer cover of a golfball, this layer may be formed from the composition of the invention.For example, an intermediate layer or inner cover layer having athickness of about 0.015 inches to about 0.06 inches may be disposedabout a core. In this aspect of the invention, the core, which has adiameter ranging from about 1.5 inches to about 1.59 inches, may also beformed from a composition of the invention or, in the alternative, froma conventional rubber composition. The inner ball may be covered by acastable thermoset or injection moldable thermoplastic material or anyof the other cover materials discussed below. In this aspect of theinvention, the cover may have a thickness of about 0.02 inches to about0.045 inches, preferably about 0.025 inches to about 0.04 inches. Thecore compression is about 30 to about 110 atti, preferably about 50 toabout 100 atti, and the overall ball compression preferably ranges fromabout 50 to about 100 atti.

When not formed from the composition of the invention, the intermediatelayer may be formed from a number of thermoplastic and thermosettingmaterials. For example, the intermediate layer(s) may be formed, atleast in part, from one or more homopolymeric or copolymeric materials,such as ionomers, primarily or fully non-ionomeric thermoplasticmaterials, vinyl resins, polyolefins, polyurethanes, polyureas, such asthose disclosed in U.S. Pat. No. 5,484,870, polyamides, acrylic resinsand blends thereof, olefinic thermoplastic rubbers, block copolymers ofstyrene and butadiene, isoprene or ethylene-butylene rubber,copoly(ether-amide), such as PEBAX, sold by Atofina Chemicals, Inc. ofPhiladelphia, Pa., polyphenylene oxide resins or blends thereof, andthermoplastic polyesters.

For example, the intermediate layer may be formed of low acid ionomers,such as those described in U.S. Pat. Nos. 6,506,130 and 6,503,156, highacid ionomers, highly neutralized polymers, such as those disclosed inU.S. Patent Publication Nos. 2001/0018375 and 2001/0019971, or mixturesthereof. The intermediate layer may also be formed from the compositionsas disclosed in U.S. Pat. No. 5,688,191. The entire disclosures of thesepatents and publications are incorporated herein by express referencethereto.

The intermediate layer may also include a wound layer formed from atensioned thread material. The thread may be single-ply or may includetwo or more plies. Suitable thread materials include, but are notlimited to, fiber, glass, carbon, polyether urea, polyether blockcopolymers, polyester urea, polyester block copolymers, syndiotactic- orisotactic-poly(propylene), polyethylene, polyamide, poly(oxymethylene),polyketone, poly(ethylene terephthalate), poly(p-phenyleneterephthalamide), poly(acrylonitrile), diaminodicyclohexylmethane,dodecanedicarboxylic acid, natural rubber, polyisoprene rubber,styrene-butadiene copolymers, styrene-propylene-diene copolymers,another synthetic rubber, or block, graft, random, alternating, brush,multi-arm star, branched, or dendritic copolymers, or mixtures thereof.Those of ordinary skill in the art are aware of the process forproducing thread materials for use with the present invention.

Golf Ball Cover Layer(s)

The cover provides the interface between the ball and a club. Propertiesthat are desirable for the cover are good moldability, high abrasionresistance, high impact resistance, high tear strength, high resilience,and good mold release, among others. The cover layer may be formed, atleast in part, from a composition of the invention. For example, thepresent invention contemplates a golf ball having a large core ofpolybutadiene and a thin cover formed from the composition of theinvention.

When the compositions of the invention are incorporated into a core orintermediate/inner cover layer, however, the cover may be formed fromone or more homopolymeric or copolymeric materials as discussed in thesection above pertaining to the intermediate layer. The cover may alsobe at least partially formed from a polybutadiene reaction product, asdiscussed above with respect to the core. Golf balls according to theinvention may also be formed having a cover of polyurethane, polyurea,and polybutadiene materials discussed in U.S. Pat. No. 6,835,794.

For example, the cover may be formed from the reaction product of anisocyanate and a hydroxy-terminated component that is cured with acuring agent to form a polyurethane. In another embodiment, the cover isformed from a reaction product of an isocyanate and an amine-terminatedcomponent that is cured with a curing agent to form a polyurea.

Layer Formation

The golf balls of the invention may be formed using a variety ofapplication techniques such as compression molding, flip molding,injection molding, retractable pin injection molding, reaction injectionmolding (RIM), liquid injection molding (LIM), casting, vacuum forming,powder coating, flow coating, spin coating, dipping, spraying, and thelike. Conventionally, compression molding and injection molding areapplied to thermoplastic materials, whereas RIM, liquid injectionmolding, and casting are employed on thermoset materials. These andother manufacture methods are disclosed in U.S. Pat. Nos. 6,207,784 and5,484,870, the disclosures of which are incorporated herein by referencein their entirety.

Cores of the golf balls of the invention may be formed by any suitablemethod known to those of ordinary skill in art. When the cores areformed from a thermoset material, compression molding is a particularlysuitable method of forming the core. In a thermoplastic core embodiment,on the other hand, the cores may be injection molded. Furthermore, U.S.Pat. Nos. 6,180,040 and 6,180,722 disclose methods of preparing dualcore golf balls. The disclosures of these patents are herebyincorporated by reference in their entirety.

The intermediate layer and/or cover layer may also be formed using anysuitable method known to those of ordinary skill in the art. Forexample, an intermediate layer may be formed by blow molding and coveredwith a dimpled cover layer formed by injection molding, compressionmolding, casting, vacuum forming, powder coating, and the like.

The use of various dimple patterns and profiles provides a relativelyeffective way to modify the aerodynamic characteristics of a golf ball.As such, the manner in which the dimples are arranged on the surface ofthe ball can be by any available method. For instance, the ball may havean icosahedron-based pattern, such as described in U.S. Pat. No.4,560,168, or an octahedral-based dimple patterns as described in U.S.Pat. No. 4,960,281. Furthermore, the resultant golf balls preparedaccording to the invention typically will have dimple coverage greaterthan about 60 percent, preferably greater than about 65 percent, andmore preferably greater than about 70 percent.

Golf Ball Post-Processing

The golf balls of the present invention may be painted, coated, orsurface treated for further benefits. For example, golf balls may becoated with urethanes, urethane hybrids, ureas, urea hybrids, epoxies,polyesters, acrylics, or combinations thereof in order to obtain anextremely smooth, tack-free surface. If desired, more than one coatinglayer can be used. The coating layer(s) may be applied by any suitablemethod known to those of ordinary skill in the art. In one embodiment,the coating layer(s) is applied to the golf ball cover by an in-moldcoating process, such as described in U.S. Pat. No. 5,849,168, which isincorporated in its entirety by reference herein.

Any of the golf ball layers may be surface treated by conventionalmethods including blasting, mechanical abrasion, corona discharge,plasma treatment, and the like, and combinations thereof. In fact,because low surface energy, or surface tension, is a key feature ofpolysiloxanes, layers formed from the compositions of the invention maybe surface treated according to U.S. Patent Publication No.2003/0199337, the disclosure of which is incorporated in its entirety byreference herein.

Golf Ball Properties

The properties such as core diameter, intermediate layer and cover layerthickness, hardness, and compression have been found to effect playcharacteristics such as spin, initial velocity and feel of the presentgolf balls.

Component Dimensions

Dimensions of golf ball components, i.e., thickness and diameter, mayvary depending on the desired properties. For the purposes of theinvention, any layer thickness may be employed. For example, the presentinvention relates to golf balls of any size, although the golf ballpreferably meets USGA standards of size and weight. While “The Rules ofGolf” by the USGA dictate specifications that limit the size of acompetition golf ball to more than 1.680 inches in diameter, golf ballsof any size can be used for leisure golf play. The preferred diameter ofthe golf balls is from about 1.680 inches to about 1.800 inches. Themore preferred diameter is from about 1.680 inches to about 1.760inches. A diameter of from about 1.680 inches (43 mm) to about 1.740inches (44 mm) is most preferred, however diameters anywhere in therange of from 1.700 to about 1.950 inches can be used.

Preferably, the overall diameter of the core and all intermediate layersis about 80 percent to about 98 percent of the overall diameter of thefinished ball. The core may have a diameter ranging from about 0.09inches to about 1.65 inches. In one embodiment, the diameter of the coreof the present invention is about 1.2 inches to about 1.630 inches. Forexample, when part of a two-piece ball according to invention, the coremay have a diameter ranging from about 1.5 inches to about 1.62 inches.In another embodiment, the diameter of the core is about 1.3 inches toabout 1.6 inches, preferably from about 1.39 inches to about 1.6 inches,and more preferably from about 1.5 inches to about 1.6 inches. In yetanother embodiment, the core has a diameter of about 1.55 inches toabout 1.65 inches, preferably about 1.55 inches to about 1.60 inches. Inone embodiment, the core diameter is about 1.59 inches or greater. Inanother embodiment, the diameter of the core is about 1.64 inches orless.

When the core includes an inner core layer and an outer core layer, theinner core layer is preferably about 0.5 inches or greater and the outercore layer preferably has a thickness of about 0.1 inches or greater.For example, when part of a multi-layer ball according to invention, thecenter may have a diameter ranging from about 0.5 inches to about 1.30inches and the outer core layer may have a diameter ranging from about0.12 inches to about 0.5 inches. In one embodiment, the inner core layerhas a diameter from about 0.09 inches to about 1.2 inches and the outercore layer has a thickness from about 0.1 inches to about 0.8 inches. Inyet another embodiment, the inner core layer diameter is from about0.095 inches to about 1.1 inches and the outer core layer has athickness of about 0.20 inches to about 0.03 inches.

The cover typically has a thickness to provide sufficient strength, goodperformance characteristics, and durability. In one embodiment, thecover thickness is from about 0.02 inches to about 0.12 inches,preferably about 0.1 inches or less. For example, when part of atwo-piece ball according to invention, the cover may have a thicknessranging from about 0.03 inches to about 0.09 inches. In anotherembodiment, the cover thickness is about 0.05 inches or less, preferablyfrom about 0.02 inches to about 0.05 inches, and more preferably about0.02 inches and about 0.045 inches.

The range of thicknesses for an intermediate layer of a golf ball islarge because of the vast possibilities when using an intermediatelayer, i.e., as an outer core layer, an inner cover layer, or amoisture/vapor barrier layer. When used in a golf ball of the invention,the intermediate layer, or inner cover layer, may have a thickness about0.3 inches or less. In one embodiment, the thickness of the intermediatelayer is from about 0.002 inches to about 0.1 inches, preferably about0.01 inches or greater. For example, when part of a three-piece ball ormulti-layer ball according to invention, the intermediate layer and/orinner cover layer may have a thickness ranging from about 0.015 inchesto about 0.06 inches. In another embodiment, the intermediate layerthickness is about 0.05 inches or less, more preferably about 0.01inches to about 0.045 inches.

Hardness

Because the compositions of the invention may be used in any layer of agolf ball, the golf ball construction, physical properties, andresulting performance may vary greatly depending on the layer(s) of theball that include the compositions of the invention.

The cores included in golf balls of the present invention may havevarying hardnesses depending on the particular golf ball construction.In one embodiment, the core hardness is at least about 15 Shore A,preferably about 30 Shore A, as measured on a formed sphere. In anotherembodiment, the core has a hardness of about 50 Shore A to about 90Shore D. In yet another embodiment, the hardness of the core is about 80Shore D or less. Preferably, the core has a hardness about 30 to about65 Shore D, and more preferably, the core has a hardness about 35 toabout 60 Shore D. For example, when a core is formed from thecomposition of the invention, the core may have a hardness of about 40Shore to about 50 Shore D.

The intermediate layer(s) of the present invention may also vary inhardness depending on the specific construction of the ball. In oneembodiment, the hardness of the intermediate layer is about 30 Shore Dor greater. In another embodiment, the hardness of the intermediatelayer is about 90 Shore D or less, preferably about 80 Shore D or less,and more preferably about 70 Shore D or less. For example, when anintermediate layer is formed from the composition of the invention, thehardness of the intermediate layer may be about 65 Shore D or less,preferably ranging from about 35 Shore D to about 60 Shore D. In yetanother embodiment, the hardness of the intermediate layer is about 50Shore D or greater, preferably about 55 Shore D or greater. In oneembodiment, the intermediate layer hardness is from about 55 Shore D toabout 65 Shore D. The intermediate layer may also be about 65 Shore D orgreater. For example, a golf ball of the invention may include an innercover formed from a rosin-modified polymeric composition of theinvention having a hardness of about 60 Shore D to about 75 Shore D.

As with the core and intermediate layers, the cover hardness may varydepending on the construction and desired characteristics of the golfball. The ratio of cover hardness to inner ball hardness is a primaryvariable used to control the aerodynamics of a ball and, in particular,the spin of a ball. In general, the harder the inner ball, the greaterthe driver spin and the softer the cover, the greater the driver spin.

For example, when the intermediate layer is intended to be the hardestpoint in the ball, e.g., about 60 Shore D to about 75 Shore D, the covermaterial may have a hardness of about 20 Shore D or greater, preferablyabout 25 Shore D or greater, and more preferably about 30 Shore D orgreater, as measured on the slab. In another embodiment, the coveritself has a hardness of about 30 Shore D or greater. In particular, thecover may be from about 30 Shore D to about 70 Shore D. In oneembodiment, the cover has a hardness of about 40 Shore D to about 65Shore D, and in another embodiment, about 40 Shore to about 55 Shore D.In another aspect of the invention, the cover has a hardness less thanabout 45 Shore D, preferably less than about 40 Shore D, and morepreferably about 25 Shore D to about 40 Shore D. In one embodiment, thecover has a hardness from about 30 Shore D to about 40 Shore D.

Compression

Compression values are dependent on the diameter of the component beingmeasured. The Atti compression of the core, or portion of the core, ofgolf balls prepared according to the invention may range from about 30to about 110 atti, preferably about 50 to about 100 atti. In oneembodiment, the core compression is less than about 80, preferably lessthan about 75. As used herein, the terms “Atti compression” or“compression” are defined as the deflection of an object or materialrelative to the deflection of a calibrated spring, as measured with anAtti Compression Gauge, which is commercially available from AttiEngineering Corp. of Union City, N.J. Atti compression is typically usedto measure the compression of a golf ball. In another embodiment, thecore compression is from about 40 to about 80, preferably from about 50to about 70. In yet another embodiment, the core compression ispreferably below about 50, and more preferably below about 25.

In an alternative, low compression embodiment, the core has acompression less than about 20, more preferably less than about 10, andmost preferably, 0. As known to those of ordinary skill in the art,however, the cores generated according to the present invention may bebelow the measurement of the Atti Compression Gauge.

In one embodiment, golf balls of the invention preferably have an Atticompression of about 55 or greater, preferably from about 60 to about120. In another embodiment, the Atti compression of the golf balls ofthe invention is at least about 40, preferably from about 50 to 120, andmore preferably from about 50 to 100. In yet another embodiment, thecompression of the golf balls of the invention is about 75 or greaterand about 95 or less. For example, a preferred golf ball of theinvention may have a compression from about 80 to about 95.

Coefficient of Restitution

The present invention contemplates golf balls having CORs from about0.700 to about 0.850 at an inbound velocity of about 125 ft/sec. In oneembodiment, the COR is about 0.750 or greater, preferably about 0.780 orgreater. In another embodiment, the ball has a COR of about 0.800 orgreater. In yet another embodiment, the COR of the balls of theinvention is about 0.800 to about 0.815.

Alternatively, the maximum COR of the ball is one that does not causethe golf ball to exceed initial velocity requirements established byregulating entities such as the USGA. As used herein, the term“coefficient of restitution” (CoR) is calculated by dividing the reboundvelocity of the golf ball by the incoming velocity when a golf ball isshot out of an air cannon. The COR testing is conducted over a range ofincoming velocities and determined at an inbound velocity of 125 ft/s.Another measure of this resilience is the “loss tangent,” or tan δ,which is obtained when measuring the dynamic stiffness of an object.Loss tangent and terminology relating to such dynamic properties istypically described according to ASTM D4092-90. Thus, a lower losstangent indicates a higher resiliency, thereby indicating a higherrebound capacity. Low loss tangent indicates that most of the energyimparted to a golf ball from the club is converted to dynamic energy,i.e., launch velocity and resulting longer distance. The rigidity orcompressive stiffness of a golf ball may be measured, for example, bythe dynamic stiffness. A higher dynamic stiffness indicates a highercompressive stiffness. To produce golf balls having a desirablecompressive stiffness, the dynamic stiffness of the crosslinked materialshould be less than about 50,000 N/m at −50° C. Preferably, the dynamicstiffness should be between about 10,000 and 40,000 N/m at −50° C., morepreferably, the dynamic stiffness should be between about 20,000 and30,000 N/m at −50° C.

Moisture Vapor Transmission

The moisture vapor transmission of a golf ball portion formed from thecompositions of the invention may be expressed in terms of absorption,e.g., weight gain or size gain over a period of time at a specificconditions, and transmission, e.g., moisture vapor transmission rate(MVTR) according to ASTM E96-00. MVTR refers to the mass of water vaporthat diffused into a material of a given thickness per unit area perunit time at a specific temperature and humidity differential. Forexample, weight changes of a golf ball portion monitored over a periodof seven weeks in 100 percent relative humidity and 72° F. help todemonstrate which balls have better water resistance.

In one embodiment, the golf ball portions of the invention have a weightgain of about 15 grams per 100 in² per day or less at 38° C. and 90percent relative humidity. In another embodiment, the golf balls of theinvention have a weight gain of about 12.5 grams per 100 in² per day orless. In still another embodiment, the weight gain of the golf balls ofthe invention is about 7 grams per 100 in² per day or less. In yetanother embodiment, the weight gain is about 5 grams per 100 in² per dayor less. The golf balls of the invention preferably have a weight gainof about 3 grams per 100 in² per day or less.

Size gain may also be used as an indicator of water resistance. That is,the more water a golf ball takes on, the larger a golf ball becomes dueto the water enclosed beneath the outermost layer of the golf ballportion. Thus, the golf balls of the invention preferably have noappreciable size gain. In one embodiment, the size gain of the golfballs of the invention after a seven-week period is about 0.001 inchesor less.

EXAMPLES

The following examples are only representative of the methods andmaterials for use in golf ball compositions and golf balls of thisinvention, and are not to be construed as limiting the scope of theinvention in any way.

Example 1: Hydrophobic Covers Formed of the Compositions of theInvention

Hydrophobic compositions were formed according to the invention as shownbelow in Table 1. In particular, Prepolymer A is a urea prepolymer andPrepolymer B is a urethane prepolymer. The curative is a very lowmolecular weight trifunctional caprolactone polyol, in which all of thehydroxyl groups are primary.

TABLE 1 Formulation #1 Formulation #2 Prepolymer A¹   1 eq. PrepolymerB²   1 eq. Curative³ 0.95 eq. 0.95 eq. White Dispersion 4.5% 4.5%Material Hardness (Shore D) 42 44 ¹Prepolymer A is a reaction product ofH12MDI and an amine-terminated polybutadiene with a molecular weight of2000 and amine functionality of 2.0. ²Prepolymer B is a reaction productof H12MDI and an hydroxy-teminated polybutadiene with a molecular weightof 2000 and hydroxy functionality of 2.0. ³The curative is a TMPinitiated polycaprolactone with 3.0 functionality and a molecular weightof 300 (CAPA ® 3031 from Solvay).

The formulations were cast as covers conventional polybutadiene cores.In particular, Formulation #1 was used to form Invention Ball #1 andFormulation #2 was used to form Invention Ball #2. Control ball #1 wasformed with a polybutadiene core, an ionomer casing layer, and apolyurethane outer cover layer, where the polyurethane has a materialhardness of 48 Shore D. Control ball #2 was formed with a largepolybutadiene core and an ionomer outer cover layer, where the materialhardness of ionomer is 65 Shore D. The balls were tested for coefficientof restitution, impact resistance, and durability. The results are shownin Table 2 below.

TABLE 2 Invention #1 Invention #2 Control #1 Control #2 Pole/Equator1.682/1.679 1.679/1.677 1.684/1.680 1.680/1.681 Average Weight (g) 1.6131.616 1.649 1.604 COR 0.762 0.758 0.773 0.803 (@ 125 ft/s) Shear 1 1 1 0Resistance Rating

The balls were also tested for hydrophobicity or moisture resistance. Inparticular, six molded balls for each category, i.e., Invention #1,Invention #2, Control #1, and Control #2, were placed in a one galloncan filled with water. The balls remained submerged for a four-weekperiod. Weight gain and loss of coefficient of restitution measurementswere taken weekly.

As shown in FIGS. 5 and 6, after four weeks of submersion, the golfballs formed from both experimental formulations had superiorhydrophobicity versus the Control #1 and comparable hydrophobicity toControl #2. In addition, golf balls having covers cast from theexperimental formulations showed a smaller loss of COR than both of thecontrol balls.

Other than in the operating examples, or unless otherwise expresslyspecified, all of the numerical ranges, amounts, values and percentagessuch as those for amounts of materials, times and temperatures ofreaction, ratios of amounts, values for molecular weight (whether numberaverage molecular weight (“Mn”) or weight average molecular weight(“Mw”), and others in the following portion of the specification may beread as if prefaced by the word “about” even though the term “about” maynot expressly appear with the value, amount or range. Accordingly,unless indicated to the contrary, the numerical parameters set forth inthe following specification and attached claims are approximations thatmay vary depending upon the desired properties sought to be obtained bythe present invention. At the very least, and not as an attempt to limitthe application of the doctrine of equivalents to the scope of theclaims, each numerical parameter should at least be construed in lightof the number of reported significant digits and by applying ordinaryrounding techniques.

Notwithstanding that the numerical ranges and parameters setting forththe broad scope of the invention are approximations, the numericalvalues set forth in the specific examples are reported as precisely aspossible. Any numerical value, however, inherently contain certainerrors necessarily resulting from the standard deviation found in theirrespective testing measurements. Furthermore, when numerical ranges ofvarying scope are set forth herein, it is contemplated that anycombination of these values inclusive of the recited values may be used.

The invention described and claimed herein is not to be limited in scopeby the specific embodiments herein disclosed, since these embodimentsare intended as illustrations of several aspects of the invention. Anyequivalent embodiments are intended to be within the scope of thisinvention. For example, the compositions of the invention may also beused in golf equipment such as putter inserts, golf club heads andportions thereof, golf shoe portions, and golf bag portions. Indeed,various modifications of the invention in addition to those shown anddescribed herein will become apparent to those skilled in the art fromthe foregoing description. Such modifications are also intended to fallwithin the scope of the appended claims. All patents and patentapplications cited in the foregoing text are expressly incorporateherein by reference in their entirety.

What is claimed is:
 1. A method of forming a golf ball comprising a coreand a cover, comprising: providing a golf ball core; simultaneouslyreacting an isocyanate-containing component, a first isocyanate-reactivecomponent, and a curative blend to form a reaction product, wherein thefirst isocyanate-reactive component comprises a conjugated dienehydrocarbon comprising at least two functional groups comprising aminogroups, hydroxy groups, or a mixture thereof and the curative blendcomprises an amine-terminated component selected from the groupconsisting of diethylene triamine, propylene-oxide based triamine,dipropylene triamine, triethylene tetramine, and mixtures thereof and atleast one free radical initiator, wherein the reaction product comprisescrosslinks between (i) the hydrocarbons and (ii) the isocyanate groupsand the amino groups; and forming a golf ball cover about the golf ballcore with the reaction product.
 2. The method of claim 1, wherein theisocyanate-containing component comprises at least two isocyanategroups.
 3. The method of claim 1, wherein the first isocyanate-reactivecomponent comprises amine-terminated polybutadiene.
 4. The method ofclaim 3, wherein the amine-terminated polybutadiene comprises primaryamino groups at the terminal ends of the polybutadiene.
 5. The method ofclaim 1, wherein the first isocyanate-reactive component compriseshydroxy-terminated polybutadiene.
 6. The method of claim 5, wherein thehydroxy-terminated polybutadiene comprises primary hydroxy groups at theterminal ends of the polybutadiene.
 7. The method of claim 1, whereinthe at least one free radical initiator comprises peroxide.
 8. A methodof forming a golf ball comprising a core and a cover, comprising:providing a core; simultaneously reacting an isocyanate-containingcomponent, a first isocyanate-reactive component, and a curative blendto form a reaction product, wherein the first isocyanate-reactivecomponent comprises a conjugated diene hydrocarbon comprising at leastone functional amino group and at least one functional hydroxy group andthe curative blend comprises an amine-terminated component selected fromthe group consisting of diethylene triamine, propylene-oxide basedtriamine, dipropylene triamine, triethylene tetramine, and mixturesthereof and at least one free radical initiator, wherein the reactionproduct comprises crosslinks between (i) the hydrocarbons and (ii) theisocyanate groups and the amino groups; and forming a cover about thecore with the reaction product.
 9. The method of claim 8, wherein theisocyanate-containing component comprises at least two isocyanategroups.
 10. The method of claim 8, wherein the conjugated dienehydrocarbon comprises polybutadiene.
 11. The method of claim 8, whereinthe at least one free radical initiator comprises peroxide.